The present invention relates to mixtures of 1:2 cobalt complex formazan dyes with anthraquinone dyes or 1:2 chromium or 1:2 cobalt complex azo dyes, which are particularly suitable for dyeing or printing natural or synthetic textile polyamide fibre materials and in particular have very good fastness properties. The present invention furthermore relates to the novel 1:2 cobalt complex formazan dyes.
The present invention relates to dye mixtures which comprise at least one 1:2 cobalt complex dye of the formazan compound of the formula 
in which
X is substituted or unsubstituted C1-C8alkyl, phenyl, naphthyl, furyl or thienyl,
R1 and R2 independently of one another are hydrogen or substituted or unsubstituted C1-C8alkyl, phenyl or naphthyl,
m is a number from 1 to 4 and
the rings I, II, III and IV may be further substituted,
together with at least one anthraquinone dye of the formula (2) 
in which
Y is hydrogen or substituted or unsubstituted C1-C8alkyl, cyclohexyl, phenyl or 1,2,3,4-tetrahydronaphthyl and
Z is substituted or unsubstituted C1-C8alkyl, cyclohexyl, phenyl or 1,2,3,4-tetrahydronaphthyl,
and in which the ring V of the anthraquinone dye of the formula (2) may be further substituted by one or two hydroxyl groups,
or together with at least one 1:2 chromium or 1:2 cobalt complex dye of two identical or different azo compounds from the group comprising compounds of the formulae (3), (4), (5) and (6) 
in which R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15 and R16 independently of one another are hydrogen, C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, halogen, sulfo, hydroxyl, nitro, sulfamoyl or Nxe2x80x94C1-C4alkylsulfamoyl, which is unsubstituted or further substituted in the alkyl moiety part by hydroxyl or C1-C4alkoxy.
The 1:2 cobalt complex formazan dyes of the formula (1) are preferably symmetric cobalt complex dyes.
Substituents of a phenyl, naphthyl, furyl or thienyl radical X and of rings I, II, III and IV of the formazan compound of the formula (1) are, in addition to the radical of the formula xe2x80x94SO2N(R1)R2, independently of one another, for example, C1-C4alkyl, for example methyl or ethyl; C1-C4alkoxy, for example methoxy or ethoxy; unsubstituted or halogen-substituted C2-C4alkanoylamino, for example acetylamino, propionylamino or xcex1,xcex2-dibromopropionylamino; hydroxyl; sulfo; nitro; carboxyl; cyano; amino; halogen, for example fluorine, chlorine or bromine; C1-C4alkylsulfonyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy; vinylsulfonyl; xcex1-halogenoacryloylamino; radicals of the formulae xe2x80x94OR, xe2x80x94NHCORxe2x80x2, xe2x80x94COORxe2x80x3, CONHRxe2x80x2xe2x80x3 and SO2Rxe2x80x3xe2x80x3, in which R, Rxe2x80x2, Rxe2x80x3, Rxe2x80x2xe2x80x3 and Rxe2x80x3xe2x80x3 independently of one another are phenyl or naphthyl and Rxe2x80x2 can additionally be C1-C4alkyl; or triazinylamino, which can be further substituted by halogen, C1-C4alkylamino, phenylamino or Nxe2x80x94C1-C4alkyl-N-phenylamino. The phenyl or naphthyl radicals mentioned can be substituted as defined above for X and the rings I, II, III and IV, in particular by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, sulfo, nitro, carboxyl, cyano, halogen or C1-C4alkylsulfonyl which is unsubstituted or further substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy.
In addition to the radical of the formula xe2x80x94SO2N(R1)R2, preferred substituents for X and the rings I, II, III and IV of the formazan compound of the formula (1) are C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, C1-C4alkylsulfonyl, C1-C4hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl and nitro.
X is preferably phenyl, which can be substituted, for example, as defined above.
Phenyl or naphthyl radicals R1 and R2 can be unsubstituted or substituted. Examples of such substituents are C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, C1-C4alkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl, nitro, sulfamoyl and Nxe2x80x94C1-C4alkylsulfamoyl which is unsubstituted or further substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy.
C1-C8alkyl radicals X, R1 and R2 independently of one another are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl, and the corresponding radicals which are substituted, for example, by hydroxyl, C1-C4alkoxy or halogen. C1-C4alkyl, which can be substituted as defined, is preferred here.
R1 and R2 are preferably independently of one another hydrogen, C1-C8alkyl or phenyl, where the alkyl and phenyl radicals can be substituted as defined above.
R1 and R2 are preferably independently of one another hydrogen, C1-C4alkyl which is unsubstituted or substituted by hydroxyl or C1-C4alkoxy, or phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, C1-C4alkylsulfonyl, C1-C4hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl, nitro, sulfamoyl or Nxe2x80x94C1-C4alkylsulfamoyl which is unsubstituted or further substituted in the alkyl moiety by hydroxyl or C1-C4alkoxy. In particular, one of the radicals R1 and R2 is hydrogen here.
R1 and R2 are particularly preferably hydrogen, C1-C4alkyl which is unsubstituted or substituted by hydroxyl, or phenyl which is unsubstituted or substituted by sulfo, carboxyl or sulfamoyl. In particular, one of the radicals R1 and R2 is hydrogen here. R1 and R2 are especially preferably independently of one another hydrogen or C1-C4alkyl, in particular hydrogen or methyl.
m is preferably the number 1 or 2, in particular the number 2.
Substituents of phenyl radicals Y and Z are, for example:
C1-C12alkyl; C1-C4alkoxy; C2-C4alkanoylamino; hydroxyl; sulfo; nitro; carboxyl; cyano; amino; halogen; benzoylaminomethyl; chloroacetylamino; chloroacetylaminomethyl; xcex1-chloroacryloylaminomethyl; acryloylaminomethyl; or phenoxy, phenylcarbonylamino, phenylsulfonyloxy, phenylsulfonylamino, phenylsulfonylaminomethyl or N-methyl-phenylsulfonylaminomethyl, where the phenyl radicals can be further substituted as defined above for Y and Z. The radical Z furthermore can be an anthraquinone dye radical bonded via a bridge member; examples of these are the anthraquinone dyes of the following formula (11).
C1-C8alkyl radicals Y and Z independently of one another are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl, where the alkyl radicals can be substituted by phenyl and the phenyl radical can be further substituted as defined above for phenyl radicals Y and Z. Preferred substituents of the phenyl radical here are C1-C12alkyl, C1-C4alkoxy, C2-C4alkanoylamino, hydroxyl, sulfo, nitro, carboxyl, cyano, amino, halogen, benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl, a-chloroacryloylaminomethyl or acryloylaminomethyl.
Cyclohexyl radicals Y and Z independently of one another are, in addition to unsubstituted cyclohexyl, cyclohexyl substituted, for example, by C1-C4alkyl, phenylsulfonylamino or benzyl, where the phenyl radicals can be further substituted, for example, by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, sulfo or halogen.
1,2,3,4-Tetrahydronaphthyl radicals Y and Z independently of one another are, in addition to unsubstituted 1,2,3,4-tetrahydronaphthyl, the radical substituted, for example, by sulfo.
If the anthraquinone dye of the formula (2) contains one or two hydroxyl groups in ring V, these are as a rule bonded in the 1- and/or 2-position.
The total number of sulfo groups in the anthraquinone dye of the formula (2) is one or two.
C1-C4alkyl radicals R3 to R16 independently of one another are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, in particular methyl.
C1-C4alkoxy radicals R3 to R16 independently of one another are methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, in particular methoxy.
C2-C4Alkanoylamino radicals R3 to R16 independently of one another are, for example, acetylamino or propionylamino, in particular acetylamino. Halogen atoms R3 to R16 independently of one another are, for example, fluorine, chlorine or bromine, in particular chlorine.
The formazan compounds of the formula (1) are preferably compounds of the formula 
in which R1, R2 and m are as defined and preferred above; and the phenyl radicals can contain no further substituents or are further substituted as defined above for rings I, II, III and IV. Preferably, the phenyl radicals of the compound of the formula (7) may be further substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, C1-C4alkylsulfonyl, C1-C4hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl or nitro.
The formazan compounds of the formula (1) are particularly preferably compounds of the formula 
in which R1 and R1xe2x80x2 independently of one another are hydrogen or C1-C4alkyl and the phenyl radicals contain no further substituents or can be further substituted as defined above for rings I, II, III and IV. Preferably, the phenyl radicals of the compound of the formula (8) may be further substituted by C1-C4alkyl, C1-C4alkoxy, C2-C4alkanoylamino, C1-C4alkylsulfonyl, C1-C4hydroxyalkylsulfonyl, halogen, sulfo, hydroxyl, carboxyl or nitro. The phenyl radicals of the compound of the formula (8) preferably contain no further substituents.
The formazan compounds of the formula (1) are especially preferably compounds of the formula 
in which the phenyl radicals contain no further substituents or can be further substituted as defined above for the compound of the formula (8). Preferably, the phenyl radicals of the compound of the formula (8a) contain no further substituents.
Preferred anthraquinone dyes of the formula (2) are anthraquinone dyes of the formula 
in which Z1 is phenyl which is unsubstituted or substituted by C1-C12alkyl, C1-C4alkoxy, C2-C4alkanoylamino, halogen, benzoylaminomethyl, chloroacetylamino, chloroacetylaminomethyl or xcex1-chloroacryloylaminomethyl; phenyl-C1-C8alkyl, where the phenyl radical contains no further substituents or is substituted as defined for a phenyl radical Z1 under formula (9); cyclohexyl which is unsubstituted or substituted by C1-C4alkyl, phenylsulfonylamino or C1-C4alkylphenylsulfonylamino; 1,2,3,4-tetrahydronaphthyl; or a radical of the formula 
in which
W is a bridge member of the formula xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94OSO2xe2x80x94, xe2x80x94NHxe2x80x94SO2xe2x80x94, xe2x80x94CH2xe2x80x94NHxe2x80x94SO2xe2x80x94 or xe2x80x94CH2xe2x80x94N(CH3)xe2x80x94SO2xe2x80x94,
R17 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen and
R18 is hydrogen, C1-C4alkyl, C1-C4alkoxy, halogen or acryloylaminomethyl,
Y1 is hydrogen; C1-C4alkyl; phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy or halogen; phenyl-C1-C8alkyl which is unsubstituted or substituted in the phenyl ring by C1-C4alkyl, C1-C4alkoxy, halogen or benzoylaminomethyl; cyclohexyl which is unsubstituted or substituted by C1-C4alkyl; or 1,2,3,4-tetrahydronaphthyl, or anthraquinone dyes of the formula 
in which Z2 is phenyl which is unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy or halogen or cyclohexyl which is unsubstituted or substituted by C1-C4alkyl or benzyl and Y2 is C1-C4alkyl or is as defined above for Z2, or anthraquinone dyes of the formula 
in which R19 and R20 are hydrogen or methyl.
Particularly preferred anthraquinone dyes of the formula (2) are anthraquinone dyes of the formula 
1:2 chromium or 1:2 cobalt complex azo dyes are, in particular, 1:2 cobalt complex dyes of two identical or different azo compounds from the group comprising compounds of the formulae (3), (4) and (5), and 1:2 chromium complex dyes of two identical or different azo compounds from the group comprising compounds of the formulae (5) and (6).
Particularly preferred 1:2 chromium or 1:2 cobalt complex azo dyes are dyes of the formula 
Especially preferred dye mixtures are those which comprise, in addition to the 1:2 cobalt complex formazan dye, at least one dye of the formulae (9), (10), (11) and (43) to (50), in particular at least one dye of the formulae (12) to (50). The dye of the formula (50) is especially preferred here. The 1:2 cobalt complex formazan dye here is as defined and preferred above.
The anthraquinone dyes of the formula (2) and the 1:2 chromium and 1:2 cobalt complex azo dyes are known or can be obtained analogously to known compounds. Thus, anthraquinone dyes of the formula (2) can be obtained, for example, analogously to processes defined in GB-A-903 590, GB-A-945 806, GB-A-2 009 214 and U.S. Pat. No. 3,491,125. The 1:2 chromium and 1:2 cobalt complex azo dyes can be obtained, for example, analogously to processes defined in GB-A-716 753, GB-A-719 274, GB-A-745 641 and GB-A-851 861.
Some of the 1:2 cobalt complex formazan dyes of the formula (1) are novel. The 1:2 cobalt complex formazan dyes of the formula (1) can be obtained analogously to the process defined for the preparation of the novel 1:2 cobalt complex formazan dyes.
The dye mixture according to the invention can be prepared, for example, by mixing the individual dyes. This mixing process is carried out, for example, in suitable mills, for example bead and pinned disc mills, and in kneaders or mixers.
The dye mixtures furthermore can be prepared, for example, by spray drying the aqueous dye mixtures.
The dye mixtures preferably comprise 5 to 95% by weight, in particular 10 to 90% by weight and preferably 20 to 80% by weight, of the 1:2 cobalt complex formazan dye, based on the total amount of the dyes of the mixtures.
If they contain sulfo groups, the individual dyes are present in the dye mixtures according to the invention either in the form of their free sulfonic acid or, preferably, as salts thereof, for example alkali metal, alkaline earth metal or ammonium salts or as salts of an organic amine. Examples are the sodium, lithium or ammonium salts or the salt of triethanolamine. Counter-ions of metal complex dyes having a negative charge are, for example, the cations of the abovementioned salts.
The dye mixtures as a rule contain further additives, for example sodium chloride or dextrin.
The invention furthermore relates to a process for dyeing or printing fibre materials containing hydroxyl groups or containing nitrogen using the dye mixtures according to the invention.
Fibre materials are preferably both natural polyamide fibre materials, for example silk or, in particular, wool, and synthetic polyamide fibre materials, for example polyamide 6 or polyamide 6.6, or wool- or polyamide-containing blend fabrics. Synthetic polyamide fibre materials are of particular interest here.
The fibre material mentioned can be in widely varying processing forms, for example as fibres, yarn, woven fabric or knitted fabric, and in particular in the form of carpets.
The dyeing or printing can be carried out in customary dyeing or printing apparatuses. The dye liquors or printing pastes can comprise further additives, for example wetting agents, antifoams, levelling agents or agents which influence the property of the textile material, for example softening agents, additives for flameproofing or soil-, water- and oil-repellent agents, as well as water-softening agents and natural or synthetic thickeners, for example alginates and cellulose ethers.
The dye mixtures according to the invention give level dyeings having good all-round properties, in particular good fastness to rubbing, wet processing, wet rubbing, light and hot light. The dye mixtures according to the invention furthermore have a good water-solubility and resistance to hard water and are distinguished by good affinity properties and good combinability with other dyes.
The invention furthermore relates to symmetric 1:2 cobalt complex formazan dyes of compounds of the formula 
in which
R21 is hydrogen, halogen or C1-C4alkylsulfonyl which is unsubstituted or hydroxyl-substituted and
a) A1 is a radical of the formula 
B1 is a radical of the formula 
in which
R22 is hydrogen or unsubstituted or hydroxyl-substituted C1-C4alkyl,
R22xe2x80x2 is hydrogen or C1-C4alkyl,
R23 and R23xe2x80x2 independently of one another are each hydrogen, C1-C4alkyl or halogen,
R24 is C1-C4alkanoylamino or Nxe2x80x94C1-C4alkylsulfamoyl which is unsubstituted or substituted in the alkyl moiety by hydroxyl,
R25 is hydrogen or halogen and
R26 is hydrogen, unsubstituted or hydroxyl-substituted C1-C4alkyl or phenyl which is unsubstituted or substituted by sulfo, carboxyl or sulfamoyl, or
b) A1 is a radical of the formula 
B1 is a radical of the formula 
in which
R27 is hydrogen or halogen,
R28 is hydrogen or sulfamoyl and
R25 and R26 independently are as defined above.
C1-C4alkyl here is generally methyl, ethyl, n- or iso-propyl or n, iso-, sec- or tert-butyl, and preferably methyl or ethyl. Examples of unsubstituted or hydroxyl-substituted C1-C4alkyl are, in particular, methyl, ethyl or 2-hydroxyethyl. Halogen is generally, for example, fluorine, bromine or, in particular, chlorine. Examples of unsubstituted or hydroxyl-substituted C1-C4alkylsulfonyl are methylsulfonyl, ethylsulfonyl or 2-hydroxyethylsulfonyl. Examples of C1-C4alkanoylamino are acetylamino or propionylamino.
Preferred embodiments of the present invention relate to:
a) symmetric 1:2 cobalt complex formazan dyes of compounds of the formula 
in which R21 is hydrogen, chlorine or fluorine, R22 is hydrogen, methyl, ethyl or 2-hydroxyethyl,R25 is hydrogen or chlorine and R26 is hydrogen, methyl, ethyl, 2-hydroxyethyl, phenyl, 2- or 3-carboxyphenyl, 2- or 3-sulfamoylphenyl or 2- or 3-sulfophenyl.
b) symmetric 1:2 cobalt complex formazan dyes of compounds of the formula (51a) defined above, in which R21 is hydrogen, chlorine or fluorine, R22 is hydrogen, methyl or ethyl, R25 is chlorine and R26 is hydrogen, methyl, ethyl, 2-carboxyphenyl, 2-sulfamoylphenyl or 2-sulfophenyl.
c) symmetric 1:2 cobalt complex formazan dyes of compounds of the formula 
in which R21 is hydrogen or chlorine, R22xe2x80x2 is hydrogen, methyl or ethyl, R24xe2x80x2 is N-methylsulfamoyl, N-ethylsulfamoyl or N-2-hydroxyethylsulfamoyl, R25 is hydrogen or chlorine and R26 is hydrogen, methyl or ethyl.
d) symmetric 1:2 cobalt complex formazan dyes of compounds of the formula (51b) defined above, in which R21 is hydrogen, R22xe2x80x2 is hydrogen, R24 is acetylamino or, in particular, propionylamino, R25 is hydrogen or chlorine and R26 is hydrogen, methyl or ethyl.
e) symmetric 1:2 cobalt complex formazan dyes of compounds of the formula 
in which R21 is hydrogen, methylsulfonyl, ethylsulfonyl or 2-hydroxyethylsulfonyl, R25 is hydrogen or chlorine, R26 is hydrogen, methyl, ethyl, 2-sulfophenyl, 2-carboxyphenyl or 2-sulfamoylphenyl, R27 is hydrogen or chlorine and R28 is hydrogen or sulfamoyl.
f) Symmetric 1:2 cobalt complex formazan dyes of the formula 
in which M⊕ is a cation. A cation M⊕ is, for example, a proton or, preferably, a metal cation, for example an alkali metal cation, such as Na⊕, K⊕ or Li⊕ furthermore can be an ammonium cation or the ammonium salt of an organic amine, for example the salt of mono-, di- or triethanolamine.
The compounds of the formula (51) can be prepared in a manner which is known per se, for example by diazotizing a compound of the formula
B1xe2x80x94NH2xe2x80x83xe2x80x83(57),
coupling the product to the hydrazone of the formula 
and metallizing the resulting metal-free compound with a cobalt salt, in which the variables R21, A1 and B1 are as defined under formula (51).
The diazotization of the amine of the formula (57) is as a rule carried out by the action of nitrous acid in aqueous-mineral acid solution at a low temperature, and the coupling to the coupling component of the formula (58) is advantageously carried out at alkaline pH values, for example at pHxe2x89xa79 and in particular at a pH of 10 to 12.
The metallization takes place, for example, in an aqueous medium which has an alkaline pH, for example a value of 7.5 to 12, and preferably 8 to 12, at a temperature of 40 to 100xc2x0 C., and in particular at 40 to 60xc2x0 C. Suitable cobalt salts are, for example, the acetate, nitrate, chloride or, in particular, the sulfate.
The coupling of the diazotized compound of the formula (57) to the compound of the formula (58) and the metallization can be carried out in succession or also simultaneously, for example by adding the diazo suspension together with the cobalt salt to the solution of the hydrazone.
The compounds of the formulae (57) and (58) are known per se or can be prepared analogously to known compounds.
The dyes according to the invention as a rule contain further additives, for example sodium chloride or dextrin.
The invention furthermore relates to a process for dyeing or printing fibre materials containing hydroxyl groups or containing nitrogen with the dyes according to the invention.
Preferred fibre materials are both natural polyamide fibre materials, for example silk or, in particular, wool, and synthetic polyamide fibre materials, for example polyamide 6 or polyamide 6.6, or wool- or polyamide-containing blend fabrics. Synthetic polyamide fibre materials are of particular interest here.
The fibre material mentioned can be in widely varying processing forms, for example as fibres, yarn, woven fabric or knitted fabric, and in particular in the form of carpets.
The dyeing or printing can be carried out in customary dyeing or printing apparatuses. The dye liquors or printing pastes can comprise further additives, for example wetting agents, antifoams, levelling agents or agents which influence the property of the textile material, for example softening agents, additives for flameproofing or soil-, water- and oil-repellent agents, as well as water-softening agents and natural or synthetic thickeners, for example alginates and cellulose ethers.
The dyes according to the invention give level dyeings having good all-round properties, in particular good fastness to rubbing, wet processing, wet rubbing, light and hot light. The dyes according to the invention furthermore have a good water-solubility and resistance to hard water and are distinguished by good affinity properties and by good combinability with other dyes.
In the following examples, parts are by weight. The temperatures are degrees Celsius. Parts by weight bear the same relation to parts by volume as the gram to the cubic centimeter.